Dyeing, printing, or stenciling of acetyl cellulose or products made therewith



Patented Nov. '6, 1928.

UNITED STATES r 1,690,481 PATENT OFFICE.

GEORGE HOLLAND ELLIS AND WILLIEAM OAKLAND GOLD'IHORPE, OF SPONDON, NEAR DERBY, ENGLAND, ASBIGNORS TQ CELANESE CORPORATION 01 AMERICA, A COB- PORA'IION OF DELAWARE.

DYEING, PRINTING, OR STENCIDING OI ACETYL CELLULOSE OR PRODUCTS IADE THEREWITH.

No Drawing. Application filed August 6, 1925, Serial No. 48,666, and in Great Britain August 14, 1924,

This invention relates to the dyeing, printing or stenciling (all hereinafter in the claims included in the term dyein of cellulose acetate or yarns, threads, fa rics, films or other goods or products made therewith.

In a previous U. S. application S. No. 664,7 80 filed September 25, 1923, Patent No. 1,618,413, George Holland Ellis has. described processes for dyeing, printing or stenciling of cellulose acetate or yarns, threads, fabrics, films or other goods or prod? ucts made therewith by means of any colourin matters or organic compounds having a nity for cellulose acetate or capable of colouring the same, but which are insoluble, practically insoluble or of relatively low solubility in Water, said colouring. matters or or- 'ganic compounds being employed according to the said application in the form of soluble or more soluble modifications obtained by treating them, prior to addition to the dyeb-aths or preparations for printing or otherwise colouring, with sulphorioinoleic or other sulphated fatty acids or other bodies having oily or fatty characteristics, namely higher fatty acids or sulphonated or other derivatives thereof containing salt-forming groups (e. g. the sulpho group or carboxyl group or both sulpho and carboxyl groups) or with salts of any of such bodies, for instance their alkali or ammonium salts. All such bodies and their salts are hereinafter and are in the specification of said U. S. application included in the term bodies of oily or 'fatty characteristics.

For example in the said application S. No. 664,780, George Holland Ellis has described how insoluble, relatively insoluble or relatively low-soluble colouring matters or organic compounds such for example as the following may be'solubilized by the said bodies of oily or fatty characteristics and applied for dyeing or otherwise colouring cellulose acetate or goods made therewith: N on-sulphonated or other relatively insoluble derivatives of the azo class containing or not containing primary or secondagy or tertiary amino groups such as alkylate or arylated' amido groups or substituent groups such as nitro, chlor, ethoxy or methoxy groups; simple amino bases for application according to the azoic method) such as paranitraniline, metanitraniline, benzidine, d methylaniline, alpha naphthylamine or diphenylamine; unreduced colouring matters of the aryl or substituted aryl benzo or naphthoquinone monoimide series generally dianisidine,

comprised within the term indophenols; in-

Further in U. S. application S. No. 7 37 .903,

filed 15 September, 1924, George Holland Ellis, F. M. Stevenson and C. M. Croft have described inter alia how'non-sulphonated derivatives of the pyrazolone series, e. g. unsulphonated' a-zo derivatives of pyrazolone compounds may be solubilized by the aforesaid bodies of oily or fatty characteristics and applied for dyeing, printing or stenciling cellulose acetate or goods made therewith. Further in U. S. application S. No. 740,413, filed 27 September, 1924, 1,600,277 George Holland Ellis has described the application for dyeing, printing or stenciling yarns, fabrics or other products consisting of or containing cellulose acetate, of vat dyes of the anthraquinone series applied in the unreduced state, solubilized by the said bodies of oily or. fatty characteristics. Said vat dyes comprise the various dyes marketed under the trade marks Indanthrene, Cibanone, Algol, Helind'one and any other vat dyestuffs of the anthraquinone series.

Further in U. S. application S. No. 6,460, filed 2 February, 1925, the said George Holland Ellis has described inter alia how intives of diarylamines may be solubilized by the aforesaid bodies of oily or fatty characteristics and applied for dyeing, printing or stenciling cellulose acetate or goods made therewith. I

Now We have found that'by using certain -=soluble or relatively insoluble nitro derivabodies which We hereinafter term secondary or auxiliary solvents, in' conjunction with the fill aforesaid bodies of oil or fatty characteristics (which term as be ore mentioned also includes their salts) for solubilizing or converting into more soluble modifications any of the water-insoluble or insufficiently water-soluble colouring matters or organic compounds having an afiinity for or capable of colouring cellulose acetate, all of which are hereinafter in the claims included in the term relatively water-insoluble organic compounds capable of coloring cellulose acetate, greatly improved results may be obtained. Such secondary or auxiliary solvents comprise a wide range of chemical compounds, and those we have found especially useful comprise alkyl or alkylene halides, all hereinafter termed halogen derivatives of aliphatic hydrocarbons, such for instance as tetrachlorethane, trichlorethylene; simple or mixed derivatives of the cyclic or aromatic series containing one or more amino, chlor or hydroxy roups, such for example as cresols, alkylanllines, toluidines, chlorphenols, mono or poly chlor benzene-s; hydrogenated derivatives of such or other aromatic compounds such for example as hexahydrophenol, hexahydrocresols, hexahydrobenzene, dekahydro-naphthalene, tetrahydro-napthalene and the like. Any other bodies having a similar effect of giving an enhanced solubilizing action in conjunction with the bodies of oily or fatty characteristics may however be employed.

According to the present invention the secondary or auxiliary solvents may be used in conjunction with the bodies of oily or fatty characteristics for the solubilization of any of the insoluble or insufficiently soluble colouring matters or organic compounds having aflinity for cellulose acetate, and the solubilized coloring matters or compounds may be employed for the dyeing, printing, or stenciling of the cellulose acetate or goods made therewith.

By the employment of the auxiliary solvents it is possible to obtain dyeings, printings or stencilings of improved de th of shade for agiven quantity of dyestu or colouring matter or compound, or to effect considerable economy in the quantities of dyestuffs, colouring matters or compounds required for a given depth of shade. The auxiliary solvents are of especial use in the solubilization of highly insoluble colouring matters or organic compounds which have hitherto required very large quantities of the aforesaid bodies of oily or fatty characteristics or salts thereof for their solubilization and practical application. In such cases especially it has been found that the use of such secondary or auxiliary solvents together with the bodies of oily or fatty characteristics enables dyeings, printings or stencilings of greatly improved depth of shade, penetration, levelness and clarity to be obtained, and this often with great saying of the bodies of oily or fatty characteristics. Also economv may be obtained in the amount of dyestuffs or compounds r uired for a given depth of shade.

uch high y insoluble colouring matters or organic compounds comprise many chemical types of which the following are some examples: azo and polyazo compounds, anthraquinone derivatives, indigoid derivatives, nitrodiarylamine derivatives, for instance 2-4 dinitrobenzene azo diethylaniline, paranitrobenzene azo beta naphthol, benzene azo benzene azo betanaphthol, symmetrical di-paratolyl 1: 4 diamino anthraquinone, 1 hydroxy 4: paratolylamino anthraquinone, 1: paratolylamino 4 methylamino anthraquinone, 4 paratolylamino 1-anthraquinone-N-methyl pyridone, 2:4 dinitrodiphenylamine, 2:4 dinitro 3 hydroxy-diphenylamine, diparamethoxybenzoyl diamino anthrarufin, 44" dimethoxy 2 6 dialpha anthraquinonyl-diamino anthraquinone, 3- (5 7 dibrome-indole) -2-thionaphthenindigo. The use of the aforesaid secondary or auxiliary solvents enables greatly improved results to be obtained with the unreduced so-called vat colours.

Also in many cases the employment of the auxiliary solvents enables a substantial saving to be effected in the quantity of dyestuffs or compounds required for the production of a given depth of shade.

With reference to the application of the invention for dyeing, printing or stenciling the materials by means of the azoic process, that is to say wherein the actual dyestuff is produced on the cellulose acetate fibre or material by coupling of bases and developers on the material, it is understood that the expression organic compounds capable of coloring cellulose acetate employed hereinafter in the claims, applies to the said bases or developers in the sense that they are capable of coloring the cellulose acetate by such production of a dye thereon, whether or not the bases or developers themselves color cellulose acetate.

In carrying out the invention one or more of the insoluble or insufficiently soluble or relatively insoluble colouring matters or organic compounds having affinity for cellulose acetate or capable of colouring the same, may be treated with one or more of the aforesaid bodies of oily or fatty characteristics and one or more of the aforesaid secondary or auxiliary solvents, in any order separately, or together inv admixture, at any suitable temperature or pressure, in presence or absence of water. It is to be understood that the phraseology hereinafter employed in the claims pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with at least one auxiliary solvent and the corresponding phrase ology employed in the other claims in terms of more specific bodies of these classes, is to be read in this broad sense. The solubilized modifications thus obtained may be then ill) Iii-1 added to the dyebaths, printing pastes or other preparations and the application to the goods be performed by methods commonly known in the arts.

The following are some examples illustrating how the invention may be performed, it being understood that these are given only by way of illustration and in no way as limitative, and that the colouring matters or compounds, solubilizing agents and auxiliary solvents, proportions, temperatures and other conditions and the manner of operation may be varied widely.

Example I.

' to the dyebath through the usual filter cloths or sieves. The resultant dyebath will yield a bright shade of red on 100 lb. of acetyl cellulose in the form of yarn in hanks.

Example [1.

lb. of'2 4 dinitro 4 aminodiphenylamine is ground up with about 4 lb. of 50% sodium salt of sulphoricinoleic acid and heated; about 2 lb. of hexahydrophenol are added and the heating continued with stirring till a clear mass is obtained. This is then diluted by pouring into 25 gallons of cold soft Water and stirring well. This liquor is then added to the aqueous dyebath contained in a suitable dyeing machine, and the resultant bath will yield a full old gold shade on 50 lb. fabric knitted from acetyl celluose yarn.

Example 11!.

1 lb. of 3-( 5:7 dibromoindole)-2'-thionaphthen-indigo, is pasted with about 4 lb. of tetrachlorethane and heated to C. This is then poured into 10 lb. of 50% aqueous sodium salt of sulphoricinoleic acid. The whole is again heated-with stirring and then poured into 40 galls. of soft water at about 50 C. On adding this to the dyebath the same will then be suitable for dyeing a bright fast rose shade on lb. of acetyl cellulose yarn or fabric.

Example IV.

2 lb. of 4-paratolylamino l-anthra N- methyl-pyridone are pasted up with 8 lb. of tetrachlorethane and heated until dissolved. This hot solution is then poured into 16 lb. of hot 50% aqueous sodium salt of sulphori'cinoleic acid and heating continued. The whole liquor isthen added to the dyebath which is capable of yielding a fast violet-red shade on 200 lb. of acetyl cellulose yarn in the form of hanks etc.

If the colouring matter or compound applied according to the rocess of the present invention contains diazotizable primary amino roups, it may be diazotizcd and de velope on the material in the usual manner to form a further dyestufi or dyestuffs.

When dyeings -or colourings are to be produced by the uzoic process, i. e. the production of a dyestuif on the material by coupling of bases and developers on the material, the insoluble component (whether base or developer) may be solubilized and applied by the process of the present invention, either component being applied first to the material.

When the azoic process is employed it is understood that the auxiliary solvent employed should not itself be capable of acting as a component in such a manner as to affect the shade to be produced.

Other colouring matters not deleteriously affected by the process of the present invention may, if desired, be dyed, printed or stenciled on the material, together with the colouring matters or compounds of the character before indicated.

Mixed goods may be dyed, printed or stenciled in uniform or contrasting effects with or without employment of other dyestufi's, compounds or components, according to the character of the non-acetate portion of the goods, said other dyestuffs or components being applied if desired before or after the application of the aforesaid insoluble or relatively insoluble dyestuffs, compounds or com ponents or, when not deleteriously affected by the solubilizing-agents, they may if desired be applied in conjunction with the aforesaid insoluble or relatively insoluble colouring matters, compounds or components.

What we claim and desire to secure by Letters Patent is 1. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the from of solubilized modifications obtained by pret-reating them with a solubilizing agent comprising a body of oily or fatty characteristics and with at least one auxiliary solvent.

2. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them Hill treating said materials with relatively water' insoluble organic compounds capable of coloring cellulose acetate, said organic compounds bein employed in the form of solubilized modlfications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with at least one auxiliary solvent.

4. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic -compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with 'a halogen derivative of an aliphatic hydrocarbon.

5. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with a halogen derivative of an aliphatic hydrocarbon.

6. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them. with a solubilizing agent comprising sodium salt of sulphoricinoleie acid and with a halogen derivative of an aliphatic hydrocarbon.

7. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of colorin cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with tetrachlorethane.

8. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with tctraehlorethane.

9. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modificationsnbtained by pretreating them with a solubilizing agent comprisin sodium salt of sulphoricinoleic acid and wit 1 tetrachlorethane.

10. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with unreduced. vat dyestu s capable of coloring cellulose acetate, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with at least one auxiliary solvent.

11. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced vat dyestufis capable of coloring cellulose acetate, said dyestufls being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with at least one auxiliary solvent.

12. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced vat dyestuffs capable of coloring cellulose acetate, said dyes-tufts being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with at least one auxiliary solvent.

13. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with unreduced vat dyestu s capable of coloring cellulose acetate, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with a halogen derivative of an aliphatic hydrocarbon.

14. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced vat dyestuffs capable of coloring cellulose acetate, said d estufi's being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with a halogen derivative of an aliphatic hydrocarbon.

15. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with unreduced vat dyestuils capable of coloring cellulose acetate, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with a halogen derivative of an aliphatic hydrocarbon.

16. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with unreduced vat dyestu s capable of coloring cellulose acetate, said dyestufis being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body'of oily or fatty characteristics and with tetrachlorethane.

17. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with unreduced vat dyestu s capable of coloring cellulose acetate, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with tetrachlorethane.

18. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced Vat dyestuffs capable of coloring cellulose acetate, said dyestuifs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent com prising sodium salt of sulphoricinoleic acid and with tetrachlorethane.

19. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with at least one auxiliary solvent.

20. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with at least one auxiliary solvent.

21. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuflfs, said dyestuffs bein employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with at least one auxiliary solvent.

22. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestufl's bein employed in the form of solubilized mo ifications obtained by pretreating them with a solubilizing agent comprisin a body of oily or fattycharacteristics, andl with a halogen derivative of an aliphatic hydrocarbon.

23. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestufis, said dyestufi's being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with a halogen derivative of an aliphatic hydrocarbon.

24. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestufis being employed in the form of solubizilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with a halogen derivative of an aliphatic hydrocarbon.

25. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics and with tetrachlorethane.

26. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestufl's, said dyestuffs being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphoricinoleic acid and with tetrachlorethane.

27. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with unreduced indigoid vat dyestuffs, said dyestuffs being em ployed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoricinoleic acid and with tetrachlorethane.

28. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with 3- (5 7 -dibromoindole)-2-thionaphthenindigo, said organic com ound bein employed in the form of a solu ilized modification obtained by pretreating it with a solubilizing agent comprisin a body of oily or fatty characteristics and with at least one solvent.

29. A processfor the dyeing of materials comprising cellulose acetate which comprises treating said materials with 3-(5 :7 dibromoindole)-2-thionaphthenindigo, said organic compound bein employed in the form of a solubilized modification obtained by pretreating it with a solubilizing agent comprisin sodium salt of sulphoricinoleic acid and with tetrachlorethane.

In testimony whereof we have hereunto subscribed our names.

GEORGE autumn nus, WILLIAI ouumn comment. 

